Biocementation Methods and Systems

ABSTRACT

The invention is directed to kits, compositions, tools and methods comprising a cyclic industrial process to form biocement. In particular, the invention is directed to materials and methods for decomposing calcium carbonate into calcium oxide and carbon dioxide at an elevated temperature, reacting calcium oxide with ammonium chloride to form calcium chloride, water, and ammonia gas; and reacting ammonia gas and carbon dioxide at high pressure to form urea and water, which are then utilized to form biocement. This cyclic process can be achieved by combining industrial processes with the resulting product as biocement. The process may involve retention of calcium carbonate currently utilized in the manufacture of Portland Cement.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.16/153,362 filed Oct. 5, 2018, which issued as U.S. Pat. No. 11,008,591on May 18, 20921, which claims priority to U.S. Provisional ApplicationNo. 62/568,533 filed Oct. 5, 2017, and U.S. Provisional Application No.62/735,062 filed Sep. 22, 2018, the entirety of each of which isspecifically and entirely incorporated by reference.

BACKGROUND 1. Field of the Invention

The invention is directed to kits, compositions, tools and methodscomprising a cyclic industrial process for forming biocement. Inparticular, the invention is directed to materials and methods fordecomposing calcium carbonate into calcium oxide and carbon dioxide atan elevated temperature, reacting calcium oxide with ammonium chlorideto form calcium chloride, water, and ammonia gas; and reacting ammoniagas and carbon dioxide at high pressure to form urea and water, whichare then utilized to form biocement.

2. Description of the Background

Global industrial production of ammonia in 2014 was 176 million tons, a16% increase over the 2006 production of 152 million tons. Industrialammonia production is responsible for 1.44% of global CO2 emissions.Ammonia production consumes 5% of global natural gas production, andconsumes about 2% of global energy production.

The biocementation reaction (see FIG. 1) relies on the metabolichydrolysis of urea, producing ammonium and carbonate ions in a solutioncontaining calcium chloride.

2(NH₂)CO+CaCl₂+2H₂O

2NH₄Cl+CaCO₃

Calcium cations react with the carbonate anions at the surface of thebacterial membrane, forming calcium carbonate of the polymorph calcite.Ammonium cations and chloride anions remain in balance in the processwater.

Calcium chloride is produced by reacting calcium oxide with ammoniumchloride to produce calcium chloride, water, and ammonia gas.

CaCO₂₊NH₄Cl→CaCl+H₂O+NH₄

The Solvay process or ammonia-soda process is an industrial process forthe production of sodium carbonate, also referred to as soda ash, andcalcium chloride. The chemical process can be written as:

2NaCl+CaCO₃→Na₂CO₃+CaCl₂

Ingredients for this process are readily available and include salt andlimestone. Solvay-based chemical plants now produce roughlythree-quarters of the world-wide supply, with the remainder providedfrom natural deposits.

Urea production, also called the Bosch-Meiser urea process after itsdiscoverers, involves two main equilibrium reactions with incompleteconversion of the reactants. The first is carbamate formation: the fastexothermic reaction of liquid ammonia with gaseous carbon dioxide (CO₂)at high temperature and pressure to form ammonium carbamate:

2NH₃+CO₂

H₂N—COONH₄

The second is urea conversion: the slower endothermic decomposition ofammonium carbamate into urea and water:

H₂N—COONH₄

(NH₂)₂CO+H₂O

The overall conversion of NH₃ and CO₂ to urea is exothermic, thereaction heat from the first reaction driving the second. Like allchemical equilibria, these reactions behave according to Le Chatelier'sprinciple, and the conditions that most favor carbamate formation havean unfavorable effect on the urea conversion equilibrium. Therefore,conventional process conditions involve a compromise: the ill-effect onthe first reaction of the high temperature (around 190 C) needed for thesecond is compensated for by conducting the process under high pressure(140-175 bar), which favors the first reaction.

Although typically necessary to compress gaseous carbon dioxide to thispressure, the ammonia is available from the ammonia plant in liquidform, which can be economically pumped into the system. As ureaconversion is incomplete, the product is separated from unchangedammonium carbamate.

In urea production plants this was done by letting down the systempressure to atmospheric to let the carbamate decompose back to ammoniaand carbon dioxide. Originally, because it was not economic torecompress the ammonia and carbon dioxide for recycle, the ammonia atleast would be used for the manufacture of other products, for exampleammonium nitrate or sulfate which vented the carbon dioxide as waste.Later process schemes made recycling unused ammonia and carbon dioxidepractical. This was accomplished by depressurizing the reaction solutionin stages (first to 18-25 bar and then to 2-5 bar) and passing it ateach stage through a steam-heated carbamate decomposer, recombining theresultant carbon dioxide and ammonia in a falling-film carbamatecondenser and pumping the carbamate solution into the previous stage.

SUMMARY OF THE INVENTION

The present invention overcomes problems and disadvantages associatedwith current strategies and designs, and provides new tools,compositions, and methods for the manufacture of ammonia, ammoniumchloride, calcium chloride, urea, and/or calcium carbonate.

One embodiment of the invention is directed to methods of formingbiocement comprising: decomposing calcium carbonate, preferably at anelevated temperature or with acid, to form calcium oxide and carbondioxide; reacting calcium oxide with ammonium chloride to form calciumchloride and ammonia, reacting ammonia and carbon dioxide in a processto form urea and water; and reacting urea and calcium chloride in aprocess to form biocement. Preferably decomposing comprises treatingcalcium carbonate with elevated temperatures or an acid wherein thepreferred elevated temperature is about 850° C. or more and thepreferred acid comprises hydrochloric acid. Preferably the processcomprises elevated pressure, corona discharge, or co-culture withurea-producing organisms. Preferably, calcium ions and dissolved carbondioxide are obtained from seawater. Preferably, reacting urea withcalcium chloride further forms ammonium chloride.

Another embodiment of the invention is directed to methods of formingbiocement comprising: decomposing calcium carbonate, preferably at anelevated temperature or with acid, to form calcium oxide and carbondioxide; reacting calcium dioxide with ammonium in a process to formurea and water; and reacting urea and calcium chloride to formbiocement. Preferably decomposing comprises treating calcium carbonatewith elevated temperatures or an acid wherein the preferred elevatedtemperature is about 850° C. or more and the preferred acid compriseshydrochloric acid. Preferably the process comprises elevated pressure,corona discharge, or co-culture with urea-producing organisms.Preferably reacting urea with calcium chloride further forms ammoniumchloride. Preferably, ammonium chloride is further decomposing to formacid and ammonia.

Other embodiments and advantages of the invention are set forth in partin the description, which follows, and in part, may be obvious from thisdescription, or may be learned from the practice of the invention.

DESCRIPTION OF THE FIGURES

FIG. 1 The urea-hydrolysis biocementation reaction.

FIG. 2 The urea-hydrolysis biocementation reaction as a closed loopindustrial cyclic process.

FIG. 3 The urea-hydrolysis biocementation reaction as an industrialcyclic process where limestone calcium carbonate is converted intobiocement.

FIG. 4 The urea-hydrolysis biocementation reaction represented atlarge-scale industrial production volumes.

FIG. 5 The urea-hydrolysis biocementation reaction.

FIG. 6 The urea-hydrolysis biocementation reaction where process wateris recycled through the regeneration of calcium chloride, and theelectrolysis of ammonia into hydrogen and nitrogen gases.

DESCRIPTION OF THE INVENTION

Biocementation involves the metabolic hydrolysis of urea, producingammonium and carbonate ions in a solution containing calcium chloride.Calcium cations react with the carbonate anions at the surface of thebacterial membrane, forming calcium carbonate of the polymorph calcite.Ammonium cations and chloride anions remain in balance in the processwater.

The invention is directed to the surprising discovery that this reactioncan become cyclical. In one alternative, calcium carbonate is decomposedinto calcium oxide and carbon dioxide at an elevated temperature.Calcium oxide reacts with ammonium chloride to form calcium chloride,water, and ammonia gas. The ammonia gas and carbon dioxide are reactedto synthesize urea and water which are then utilized in thebiocementation process. In another alternative, calcium carbonate isdecomposed, preferably at an elevated temperature or with acid, to formcalcium oxide and carbon dioxide; reacting calcium dioxide with ammoniumin a process to form urea and water; and reacting urea and calciumchloride to form biocement. Accordingly, depending on the precursoringredients, the result can be the production of calcium carbonate,ammonia, ammonium chloride, calcium chloride, urea, and/or ammonia.Preferably reacting urea with calcium chloride further forms ammoniumchloride. Preferably, ammonium chloride is further decomposing to formacid and ammonia.

The cyclic process can be achieved using existing industrial processescombined with biocementation technologies (see e.g., FIG. 2). As theresulting product can be for the formation of biocement as a buildingmaterial, an equivalent input stream of calcium carbonate provides fuelto the process cycle (see FIG. 3). At a large industrial scale, an inputsource of calcium carbonate is mined limestone deposits, as arecurrently used in the manufacture of Portland Cement. Preferablydecomposing comprises treating calcium carbonate with elevatedtemperatures or an acid wherein the preferred elevated temperature isabout 600° C. or more, 700° C. or more, 800° C. or more, 850° C. ormore, 900° C. or more, 1,000° C. or more, or even higher temperatures.The preferred acid comprises hydrochloric acid although a variety ofacids may be utilized including, but not limited to mineral acids,organic acids, phosphoric acid, nitric acid, acetic acid andcombinations thereof. Preferably the process comprises elevated pressuresuch as, for example, greater than 100 psig, greater than 200 psig,greater than 300 psig, greater than 400 psig, greater than 500 psig, orgreater. Corona discharge may also be utilized or co-culture withurea-producing organisms. A corona discharge is an electrical dischargebrought on by the ionization of a fluid such as air surrounding aconductor that is electrically charged. A corona will occur when thestrength (potential gradient) of the electric field around a conductoris high enough to form a conductive region, but not high enough to causeelectrical breakdown or arcing to nearby objects. It is often seen as abluish (or other color) glow in the air adjacent to pointed metalconductors carrying high voltages, and emits light by the same propertyas a gas discharge lamp. This step can be performed in isolation for theproduction of bulk urea, or can be employed within the aggregate matrixfor localized urea production, consumed at the time of biocementation.

Another embodiment is to co-culture with urea-producing organisms suchas, for example, by the autotrophic metabolism of atmospheric nitrogenand carbon dioxide into urea or by the bacterial decomposition oforganic matter. Urea-producing microrganisms include, for example,various species of Pseudomonas, Delaya avenusta, Thiosphaerapantotropha, Pseudomonas stutzeri, Fragilaria crotonensis,Pseudoalteromonas sp., Pseudoalteromonas haloplanktis, Halomonasvenusta, Pseudomonas balearica, Pseudomonas stutzeri, Bacillusmegaterium. Escherichia coli, Exiguobacterium aurantiacum,Pseudoalteromonas aliena, Pseudoalteromonas luteoviolacea, variants,serotypes, mutations, recombinant forms, or combinations thereof, andother organisms and microorganisms known to those of ordinary skill inthe art.

Modern dry-process Portland Cement manufacturing utilizes a heat sourceof 1,850° C. to 2,000° C. for achieving a material sintering temperatureof 1,450° C. within a rotary kiln. Early in the manufacturing process,calcium carbonate is decomposed into calcium oxide and carbon dioxide ata temperature of 850° C. in a preheater/calciner tower, where therequired heat energy is provided through partial recovery of the rotarykiln exhaust. A calcium oxide digester, implemented as a side-chainprocess at a Portland Cement manufacturing plant, could be similarlyfueled by the unused waste heat energy from the cement rotary kiln toprocess on-site calcium carbonate. The calcium oxide, reacted withammonium chloride, produces calcium chloride, water, and ammonia gas.The ammonia gas then reacted with carbon dioxide released during theside-chain calcium oxide production produces urea and water as a carbonneutral materials recycling process. The inputs of this process arethereby ammonium chloride and calcium carbonate, with the outputmaterials of calcium chloride and urea.

In this large scale model of the urea-hydrolysis biocementationreaction, industrial production volumes are indicated whereby limestoneinput material is converted into biocement products (see FIG. 4). Themetabolic biocementation process is represented as a distributed model,where ammonium chloride, urea, and calcium chloride are used as stable,soluble materials for transport to and from an industrial materialsrecycling system whereby materials are centralized in a recycling plantthat provides distributed biocement production facilities with urea andcalcium chloride for the production of biocement construction materialsusing local aggregates. Ammonium chloride recovered from the distributedbiocement production streams is returned to the centralized materialsrecycling plant. This closes the loop by reproducing and re-distributingfresh calcium chloride and urea. Calcium chloride and urea representapproximately 75% of the total direct material cost. This large scalemodel moves the supply chain of these important materials, where thedirect costs are internally determined by operational costs of thecentralized materials recycling plant, rather than market prices from athird party supplier.

Biocement production targets implementation of the full-recycle, largescale process models have been initially determined by current scales ofindustrial urea synthesis. Urea plants are most commonly coupled withammonia production plants, where the carbon dioxide released duringammonia production is reacted with a fraction of the produced ammoniafor the formation of urea. A small, modern urea plant producesapproximately 350,000 tons of urea per year. Based on the biocementproduction input material ratio of 1 mol. urea (2NH₂CO):1 mol. calciumchloride (CaCl₂), a production of 350,000-tons urea requires acorresponding production of 326,791-tons calcium oxide (see Table 1). Anefficient US Portland Cement manufacturing plant produces over2,000,000-tons of cement per year, consuming more than 1,276,200-tonscalcium oxide.

TABLE 1 Comparative mass of process materials in large-scale model.Assumes an annual urea production of 350,000-tons. Material Molar MassMolar Ratio Production Mass Urea 60.06 g/mol 1 350,000 tons CalciumChloride 110.98 g/mol  1 646,737 tons Calcium Carbonate 100.09 g/mol  1583,257 tons Calcium Oxide 56.08 g/mol 1 326,791 tons Carbon Dioxide44.01 g/mol 1 256,469 tons Ammonium Chloride 53.49 g/mol 2 623,438 tonsAmmonia 17.03 g/mol 2 198,497 tons

Accordingly, the system can be designed for the large (or small scale)production of one or more of calcium carbonate, calcium oxide, calciumchloride, ammonium chloride, ammonia, and urea.

Another embodiment of the invention is directed to an industrial cyclicprocess. For example, the industrial cyclic process is preferably forthe production of biocement material, where calcium ions and dissolvedcarbon dioxide/carbonates are provided by seawater, industrial wastestreams, and/or naturally occurring brines. Co-culture organism group(1) produces urea from the carbon and a nitrogen substrate. Co-cultureorganism group (2) produces biocement using seawater calcium ions andorganism group (1) produced urea. Organism group (2) produced ammoniumis then used by organism group (1) as the nitrogen substrate for ureaproduction.

The industrial process is also preferably for the production of ureaand/or ammonia for use in agriculture, chemical, and manufacturingindustries, where an organism or consortia of organisms produce ureafrom a nitrogen substrate and a carbon rich media. Produced urea can beseparated and used in aqueous form, or dried into solids such aspellets, prills, or powders for downstream use. A subsequent step usinga urease producing-bacteria can hydrolyze the urea into ammonium, whichis separated as ammonia liquor or compressed ammonia gas for downstreamuse. Examples of urease-producing bacteria include, but are not limitedto Sporosarcina spp. (e.g., S. pasteurii and S. ureae), Proteus spp.(e.g., P. vulgaris and P. mirabilis), Bacillus spp. (e.g., B. sphaericusand B. megaterium), Myxococcus spp (e.g., M. xanthus), Helicobacter spp.(e.g., H. pylori), or variants, serotypes, mutations, recombinant forms,or combinations thereof. Preferably the organism are vegetative cells,although spores can be utilized and converted to vegetative cells thatproduce urease, or the extracted urease enzyme may be used without thepresence of the enzyme-producing organism. The nitrogen substrate forurea production comprises complex nitrogen sources, or gaseousatmospheric nitrogen depending on the specification of the consortia.Carbon can be supplied in any form and, for example, converted to aliquid as dissolved atmospheric carbon dioxide. The reaction may furthercomprise additional materials to be incorporated into the biocement suchas, for example, organic or inorganic material, rock, glass, wood,paper, metal, plastic, polymers, fibers, minerals or combinationsthereof

Engineered Living Marine Cement (ELMc)

Another embodiment of the invention is directed to tools, compositions,production methods, and structures for engineered living marine cement(ELMc). ELMc involves the development of a living biological concreteand/or concrete-like materials that is utilized for marine and otherapplications. ELMc materials have the capacity to self-heal (e.g.,maintenance free), mitigating common structural degradations totraditional marine concretes that result in significant maintenanceand/or replacement costs. A viable ELMc material preferably sourcesmaterials for biocement formation directly from the environment (e.g.,seawater, mine environments).

Preferably, ELMc materials employ bacteria strains that are native to oradaptable to the environment in which the structure is produced. Forexample, in a marine environment, feedstock urea and calcium is sourceddirectly from seawater. While Calcium is plentiful in seawater as amechanic of the oceanic carbon pump, urea is available in smalleramounts which may limit the rates of biocement formation. Oceanic ureaas produced by zooplankton, marine life such as, for example, fish, andmarine bacteria. For marine biocement structures, ELMc preferablyinvolves a consortia of urea-producing and urease-producing bacteria.Over 300 strains of marine bacteria were screened for urea productionand 24 were selected, which fell into seven distinct species. Strainswere further developed by selection and/or genetic engineering resultingin a number of very high levels of ELMc production. Preferably, strainswere developed for biocement formation in units during 7-day trials,using a synthetic seawater feedstock that includes no urea.

Preferred bacterial strains generate urea through two differentmetabolic pathways: (a) purine/pyrimidine metabolism and (b) cleavage ofthe amino acid L-arginine by the enzyme arginase. In the marineenvironment, these substrates remain a limiting factor, where syntheticapproaches enable the use of more plentiful carbon sources. For example,metabolic pathways are genetically engineered for the industrialproduction of L-arginine from a glucose carbon source. Similar tools andprocesses enable the utilization of alternative carbon sources,including those produced directly from dissolved inorganic carbon.

A preferred ELMc production involves the local production of urea bybacterial generation at the nucleation site of cement formation. Thisapproach eliminates the reliance on industrially produced urea andremoves urea as a feedstock component. ELMc developed synthetic biologytools and methods involves two processes and application conditions forindustrial biocement products.

Firstly, ELMc produces biocement as a maintenance activity relevant to amaterial service life of years, decades, and longer. In thismethodology, maintenance involves a gradual deposition of material intostructural damages and defects, but maintenance begins immediately.Preferably, maintenance is a continuous process. Secondly, ELMc involvessourcing necessary feedstock components directly from nitrogen-limitednatural sources such as seawater, in native concentrations, along withany other impurities or variable factors. The ELMc produced materialsare comprised of a consortia of bacteria that generates organic urea atthe site of calcium carbonate formation. Feedstocks are limited bycomponents and/or concentrations found in natural seawaters. Sustainablebiocement development, according to the disclosures herein, provide botha carbon accounting and guide life-cycle analysis (LCA) to providesustainable sources for feedstock carbon, while maintaining theperformance and commercial viability of established products.

Another embodiment of the invention is directed to methods comprising:loading a solid object with urease-producing organisms andurea-producing organisms; placing the solid object into an environmentcontaining one or more of carbon, nitrogen and calcium; and formingcalcium carbonate within the solid object. Preferably loading with theurease-producing organisms and/or the urea-producing organisms comprisescombining the solid object with dry organisms such that the organismsare retained within or on a surface of the solid object, or placing thesolid object in a composition containing the urease-producing organismsand/or the urea-producing organisms. Preferably the solid object isloaded with spores and/or vegetative cells of the urease-producingorganisms and/or the urea-producing organisms. Preferably the solidobject comprises a natural or non-natural material, recycled ormanufactured sand, ore, a brick, a block, masonry, a panel, tile, aboard, rock, stone, crushed rock, crushed stone, minerals, crushed orfractured glass, wood, jute, ash, foam, basalt, fibers, mine tailings,paper, waste materials, waste from a manufacturing process, plastics,polymers, roughened materials, and/or combinations thereof, and alsopreferably, the solid object is permeable to microorganisms. Preferably,the solid object contains one or more of carbon, nitrogen and calcium,and more preferably the environment and the solid object containsufficient quantities of carbon, nitrogen and calcium for formingcalcium carbonate. Preferably, placing comprises immersing the solidobject entirely within the environment. Preferably, the environmentcomprises an environment that promotes the proliferation of theurease-producing organisms and/or the urea-producing organisms a marineenvironment and more preferably is a marine environment. Preferably theurea-producing organisms comprise Pseudomonas, Delaya avenusta,Thiosphaera pantotropha, Pseudomonas stutzen, Fragilaria crotonensis,Pseudoalteromonas spp., Pseudoalteromonas haloplanktis, Halomonasvenusta, Pseudomonas balearica, Pseudomonas stutzeri, Bacillusmegaterium. Exiguobacterium aurantiacum, Pseudoalteromonas aliena,Pseudoalteromonas luteoviolacea, E. coli, and variants, serotypes,mutations, recombinant forms, and combinations thereof, and theurease-producing organisms comprise Sporosarcina spp., S. pasteurii, S.ureae, Proteus spp., P. vulgaris, P. mirabilis, Bacillus spp., B.sphaericus, B. megaterium, Myxococcus spp., M. xanthus, Helicobacterspp., H. pylori, and variants, serotypes, mutations, recombinant forms,and combinations thereof. Preferably the calcium carbonate is formedfrom a combination of urea produced by the urea-producing organisms thatis acted upon by urease produced by the urease-producing organisms, andin the presence of carbon, nitrogen and calcium. Preferably the calciumcarbonate is formed as a coating around the solid object (e.g, as abiofilm containing organisms and calcium carbonate), and/or is formedoutside of the solid object. Preferably the solid object containingcalcium carbonate is utilized for erosion control in the environment, asa solid support of a structure within the environment, wherein thestructure comprises building material, an electronic device, and/or acontainer. Preferably calcium carbonate is formed within, around, and/orexternal to the solid object for a period of six months or more, for aperiod of one year or more, or for a period of 5 years or more, or thecalcium carbonate is self-replicating or self-sustaining and perpetualfor the life of the solid object. In addition, such solid objects arealso self-repairing.

Another embodiment of the invention is directed to solid objectscontaining urease-producing organisms and urea-producing organisms,preferably containing calcium carbonate. Preferably the urease-producingorganisms and the urea-producing organisms are viable, and preferablythe urease-producing organisms produce urease and the urea-producingorganisms produce urea. Preferably the urease and the urea in thepresence of carbon, calcium and nitrogen form calcium carbonate.Preferably the solid object comprises a natural or non-natural material,recycled or manufactured sand, ore, a brick, a block, masonry, a panel,tile, a board, rock, stone, crushed rock, crushed stone, minerals,crushed or fractured glass, wood, jute, ash, foam, basalt, fibers, minetailings, paper, waste materials, waste from a manufacturing process,plastics, polymers, roughened materials, and/or combinations thereof.Preferably the solid object further contains supplemental materials suchas, for example, organic or inorganic material, rock, glass, wood,paper, metal, plastic, polymers, fibers, minerals or combinationsthereof.

Another embodiment of the invention is directed to compositionscomprising a viable mixture of urease-producing organisms andurea-producing organisms. Preferably the compositions contain theurease-producing organisms and the urea-producing organisms are in theform or spores and/or vegetative cells. Preferably the composition isaqueous or dry.

The following examples illustrate embodiments of the invention, butshould not be viewed as limiting the scope of the invention.

Examples Example 1 Platform Adaptability

Traditional Portland Cement manufacturing involves a 20th-Centurycentralized industrial model, where the production of cement is tied tocapital and energy intensive processes (e.g., methane fired tunnelkiln). With changes in market demands, regulatory conditions, materialresources, and global understanding of environmental impacts evolve, theadaptation of traditional cement plants, there is a need for a change ofinfrastructural for the next plant to be built. The production designdisclosed and described herein, fills that need and also provided anadaptable platform.

The production of biocement according to the disclosures here, involvestwo interrelated systems: manufacturing equipment, and the biotechnologyof biocement production. Manufacturing equipment includes equipment formaterials handling (e.g., mixing, forming, and transit equipment), andsolid-state fermentation (e.g., feedstocks and delivery), representinghard capital costs for manufacturing product. A large portion ofmaterials and infrastructure production includes bacteria and feedstockmaterials for manufacturing and provided to production sites.

A plant of this disclosure provides for adapting the feedstock chemicalsrequired for biocement production, without also requiring significantinfrastructural or capital changes to the manufacturing systems, or theneed for a costly carbon source such as methane. The processes of thisdisclosure increases sustainability, extend performance, work with localfeedstock components, reduce production costs, and is rapidlydeployable.

Other embodiments and uses of the invention will be apparent to thoseskilled in the art from consideration of the specification and practiceof the invention disclosed herein. All references cited herein,including all publications, U.S. and foreign patents and patentapplications, are specifically and entirely incorporated by reference.The term comprising, where ever used, is intended to include the termsconsisting and consisting essentially of. Furthermore, the termscomprising, including, and containing are not intended to be limiting.It is intended that the specification and examples be consideredexemplary only with the true scope and spirit of the invention indicatedby the following claims.

1. A method of performing a cyclical reaction using calcium carbonatedecomposition to form a biocement, the method comprising: decomposingcalcium carbonate forming calcium chloride and ammonia; reacting theammonia with carbon dioxide in a process to form urea; and reacting ureawith calcium chloride to form biocement.
 2. The method of claim 1,wherein decomposing forms calcium oxide and carbon dioxide, and thecalcium oxide is treated with ammonium chloride.
 3. The method of claim1, wherein decomposing comprises treating calcium carbonate withelevated temperatures.
 4. The method of claim 3, wherein the elevatedtemperature about 850° C. or more.
 5. The method of claim 1, whereindecomposing is performed with an acid.
 6. The method of claim 5, whereinthe acid comprises a mineral acid, an organic acid, hydrochloric acid,phosphoric acid, nitric acid and/or acetic acid.
 7. The method of claim1, wherein decomposing is performed by corona discharge.
 8. The methodof claim 1, wherein reacting urea with calcium chloride further formsammonium chloride.
 9. The method of claim 1, wherein reacting urea withcalcium chloride further comprises treating with urease and/orurease-producing organisms.
 10. The method of claim 9, wherein theurease-producing organisms comprise spores and/or vegetative cells. 11.The method of claim 10, wherein the urease-producing organisms compriseone or more of Sporosarcina spp., S. pasteurii, S. ureae, Proteus spp.,P. vulgaris, P. mirabilis, Bacillus spp., B. sphaericus, B. megaterium,Myxococcus spp., M. xanthus, Helicobacter spp., H. pylori, and variants,serotypes, mutations, recombinant forms, and combinations thereof. 12.The method of claim 10, further comprising reacting urea with calciumchloride in the presence of urease-producing organisms and supplementalmaterials.
 13. The method of claim 12, wherein the supplementalmaterials comprise organic or inorganic material, rock, glass, wood,paper, metal, plastic, polymers, fibers, minerals or combinationsthereof.
 14. A method comprising: decomposing calcium carbonate to formcalcium chloride and carbon dioxide, which react to form calciumdioxide; reacting calcium dioxide with ammonium in a process to formurea; and reacting calcium chloride with urea to form biocement.
 15. Themethod of claim 14, wherein decomposing comprises treating calciumcarbonate with elevated temperatures.
 16. The method of claim 15,wherein the elevated temperature is about 850° C. or more.
 17. Themethod of claim 14, wherein decomposing is performed with an acid. 18.The method of claim 17, wherein the acid comprises a mineral acid, anorganic acid, hydrochloric acid, phosphoric acid, nitric acid and/oracetic acid.
 19. The method of claim 14, wherein decomposing isperformed by corona discharge.
 20. The method of claim 14, whereinreacting calcium chloride with urea further comprises treatment withurease and/or urease-producing organisms.
 21. The method of claim 20,wherein the urease-producing organisms comprise spores and/or vegetativecells.
 22. The method of claim 21, wherein the urease-producingorganisms comprise one or more of Sporosarcina spp., S. pasteurii, S.ureae, Proteus spp., P. vulgaris, P. mirabilis, Bacillus spp., B.sphaericus, B. megaterium, Myxococcus spp., M. xanthus, Helicobacterspp., H. pylori, and variants, serotypes, mutations, recombinant forms,and combinations thereof.
 23. The method of claim 20, further comprisingreacting urea with calcium chloride in the presence of urease-producingorganisms and supplemental materials.
 24. The method of claim 23,wherein the supplemental materials comprise organic or inorganicmaterial, rock, glass, wood, paper, metal, plastic, polymers, fibers,minerals or combinations thereof.
 25. A method comprising: decomposingcalcium carbonate to form calcium oxide and carbon dioxide, wherein thecalcium oxide is treated with ammonium chloride to form calciumchloride; and reacting calcium chloride with urea to form biocement. 26.The method of claim 25, wherein decomposing comprises treating calciumcarbonate with elevated temperatures.
 27. The method of claim 26,wherein the elevated temperature about 850° C. or more.
 28. The methodof claim 25, wherein decomposing is performed with an acid
 29. Themethod of claim 28, wherein the acid comprises a mineral acid, anorganic acid, hydrochloric acid, phosphoric acid, nitric acid and/oracetic acid.
 30. The method of claim 25, wherein decomposing isperformed by corona discharge.
 31. The method of claim 25, whereinreacting urea with calcium chloride further comprises treatment withurease and/or urease-producing organisms.
 32. The method of claim 31,wherein the urease-producing organisms comprise spores and/or vegetativecells.
 33. The method of claim 32, wherein the urease-producingorganisms comprise one or more of Sporosarcina spp., S. pasteurii, S.ureae, Proteus spp., P. vulgaris, P. mirabilis, Bacillus spp., B.sphaericus, B. megaterium, Myxococcus spp., M. xanthus, Helicobacterspp., H. pylori, and variants, serotypes, mutations, recombinant forms,and combinations thereof.
 34. The method of claim 32, further comprisingreacting urea with calcium chloride in the presence of urease-producingorganisms and supplemental materials.
 35. The method of claim 34,wherein the supplemental materials comprise organic or inorganicmaterial, rock, glass, wood, paper, metal, plastic, polymers, fibers,minerals or combinations thereof.